[go: up one dir, main page]

EP2912009A1 - Process for preparing 2-methoxymethyl-1,4-benzenediamine and salts thereof - Google Patents

Process for preparing 2-methoxymethyl-1,4-benzenediamine and salts thereof

Info

Publication number
EP2912009A1
EP2912009A1 EP13786397.3A EP13786397A EP2912009A1 EP 2912009 A1 EP2912009 A1 EP 2912009A1 EP 13786397 A EP13786397 A EP 13786397A EP 2912009 A1 EP2912009 A1 EP 2912009A1
Authority
EP
European Patent Office
Prior art keywords
formula
group
compound
mixtures
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13786397.3A
Other languages
German (de)
French (fr)
Inventor
John Michael Gardlik
Monica Jo PATTEN
Garry Steven Garrett
Bryan Patrick Murphy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Noxell Corp
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP2912009A1 publication Critical patent/EP2912009A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups

Definitions

  • the present invention relates to a process for preparing primary intermediates for dyeing keratin fibers. More particularly, the invention relates to a process for preparing 2- methoxymethyl-l,4-benzenediamine (IV-a), other compounds of formula (IV), and the salts thereof.
  • Primary intermediates are used in compositions for dyeing keratin fibers.
  • Known primary intermediates include 2-methoxymethyl-l,4-benzenediamine (IV-a), other compounds of formula (IV), and the salts thereof.
  • a process for the preparation of 2-methoxymethyl-l,4-benzenediamine (IV-a), other compounds of formula (IV), and the salts thereof comprising (a) performing a carbonyl reduction of a compound of formula (I) to prepare a compound of formula (II); (b) performing an etherification of the compound of formula (II) to prepare a compound of formula (III); and (c) performing a hydrogenation of the compound of formula (III) to prepare a compound of formula (IV):
  • R 1 , R 2 , and R 3 are substituents selected from the group consisting of:
  • C-linked substituents comprise from 1 to about 10 carbon atoms and from 0 to about 5 heteroatoms selected from the group consisting of O, F, CI, N, P, Si, and mixtures thereof;
  • N-linked substituents selected from the group consisting of NA ] A 2 ; (NA 1 A 2 A 3 ) + , NA ] SA 2 , N0 2 ;
  • halogens selected from the group consisting of F, CI, Br, and I;
  • a 1 , A 2 , and A 3 are alkyl groups comprising from 1 to about 10 carbon atoms and from 0 to about 5 heteroatoms selected from the group consisting of O, F, CI, N, P, Si, and mixtures thereof;
  • R 5 is an alkyl group
  • R 6 and R 7 are selected from the group consisting of hydrogen, alkyl groups, aminoalkyl groups, hydroxyalkyl groups, and mixtures thereof.
  • compositions and methods/processes of the present invention can comprise, consist of, and consist essentially of the elements and limitations of the invention described herein, as well as any of the additional or optional ingredients, components, steps, or limitations described herein.
  • the process for the preparation of 2-methoxymethyl- 1 ,4-benzenediamine (IV-a), other compounds of formula (IV), and the salts thereof comprises (a) performing a carbonyl reduction of a compound of formula (I) to prepare a compound of formula (II); (b) performing an etherification of the compound of formula (II) to prepare a compound of formula (III); and (c) performing a hydrogenation of the compound of formula (III) to prepare a compound of formula (IV).
  • the carbonyl reduction, then etherification, and then hydrogenation may be performed successively. In another embodiment, the carbonyl reduction, then hydrogenation, and then etherification may be performed successively.
  • Carbonyl reduction may be performed on a compound of formula (I) to prepare a compound of formula (II).
  • R 1 , R 2 , R 3 , R 6 , and R 7 are as defined previously, may be independently selected, and may be identical or different.
  • Carbonyl reduction may be performed in the presence of a carbonyl reducing agent, a carbonyl reduction catalyst, and/or a solvent.
  • the carbonyl reducing agent may be selected from the group consisting of hydrazine, hydrazine hydrate, H 2 , LiAlH 4 , LiBH 4 , DIBAL-H, NaBH 4 , NaCNBH 3 , B 2 H 6 , BH 3 /THF, sodium hydrosulfite, sodium sulfide, and mixtures thereof.
  • the carbonyl reduction catalyst may be selected from the group consisting of Raney nickel, nickel, palladium, Lindlar's catalyst, cobalt, copper chromite, platinum, platinum oxide, rhenium, tin(II) chloride, titanium(III) chloride, zinc, samarium, iron, ruthenium, iridium, rhodium, and mixtures thereof.
  • the solvent may be selected from the group consisting of water, petroleum ether, pentane, acetic acid, cyclopentane, hexane, cyclohexane, benzene, toluene, 1,4-dioxane, chloroform, diethyl ether, dichloromethane, tetrahydrofuran, methyl-tetrahydrofuran, dimethylformamide, acetonitrile, dimethyl sulfoxide, n-butanol, isopropanol, n-propanol, ethanol, methanol, and mixtures thereof.
  • Carbonyl reduction may be carried out at a temperature of from about 0°C to about
  • the formula indicated by formula (I) may be prepared by inserting a nitro function into anthranilic acid or compounds thereof in the presence of a nitrating agent and/or a solvent.
  • the nitrating agent may be selected from the group consisting of nitric acid, fuming nitric acid, red fuming nitric acid, salts of nitric acid (i.e. potassium nitrate), and mixtures thereof.
  • Etherification may be performed on the compound of formula (II) to prepare a compound of formula (III).
  • R 1 , R 2 , R 3 , R 5 , R 6 , and R 7 are as defined previously, may be independently selected, and may be identical or different.
  • Etherification may be performed by an alkylation reaction in the presence of an alkylating agent, a phase transfer catalyst, a solvent, and/or a base.
  • the reaction mixture may be homogeneous or heterogeneous, may have two or more liquid phases, and/or may have any combination of liquid and solid phases.
  • the alkylating agent may be selected from the group consisting of alcohols, derivatives of alcohols (i.e. methyl methanesulfonate), (Ci-C 4 )-I, (Ci-C 4 )-Br, (Ci-C 4 )-Cl, Me 2 S0 4, and mixtures thereof.
  • the alkylating agent may be dimethyl sulfate.
  • the phase transfer catalyst may be selected from the group consisting of ammonium salts that include tetrapentylammonium bromide, tetraoctylammonium chloride, tetraoctylammonium bromide, tetrahexylammonium iodide, tetrahexylammonium chloride, tetrahexylammonium bromide, tetraheptylammonium bromide, tetraethylammonium tetrafluoroborate, tetraethylammonium chloride, tetraethylammonium bromide, tetradodecylammonium tetrafluoroborate, tetradodecylammonium chloride, tetradodecylammonium bromide, tetradecyl- trimethylammonium chloride, benzyltriethyl ammoni
  • the solvent may be selected from the group consisting of water, petroleum ether, pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1,4-dioxane, chloroform, diethyl ether, dichloromethane, tetrahydrofuran, methyl-tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, n-butanol, isopropanol, n-propanol, ethanol, methanol, and mixtures thereof.
  • the base may be selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, aluminum hydroxide, ferrous hydroxide, ferric hydroxide, zinc hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, and mixtures thereof.
  • the base may be sodium hydroxide.
  • Etherification may also be performed by a condensation reaction in the presence of a condensation catalyst and/or a solvent.
  • the condensation catalyst may be selected from the group consisting of mineral acids, Lewis Acids, aluminum chloride, titanium tetra-isopropoxide, and mixtures thereof.
  • the solvent may be selected from the group consisting of petroleum ether, pentane, cyclopentane, hexane, acetic acid, cyclohexane, benzene, toluene, 1,4-dioxane, chloroform, diethyl ether, dichloromethane, tetrahydrofuran, methyl-tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, n-butanol, isopropanol, n-propanol, ethanol, methanol, and mixtures thereof.
  • the solvent may be methanol.
  • the condensation reaction may be carried out with an inert solvent diluent and/or with heating.
  • the inert solvent diluent may be chosen to aid in the removal of water if it is capable of forming a low boiling azeotrope.
  • the condensation reaction may be carried out at reflux using a Dean Stark trap to drain off the water as it is formed and distilled off with the azeotrope.
  • the condensation reaction may also be carried out in the presence of one or more dehydrating agents which may either react with or physically bind with the water, thereby removing the water from equilibria.
  • the dehydrating agent may be selected from the group consisting of dicyclohexylcarbodiimide, molecular sieves, magnesium sulphate, and mixtures thereof.
  • R 1 , R 2 , R 3 , R 5 , R 6 , and R 7 are as defined previously, may be independently selected, and may be identical or different.
  • Hydrogenation may be performed in the presence of hydrogen, a hydrogenation catalyst, and/or a solvent.
  • the hydrogenation catalyst may be selected from the group consisting of Raney nickel, nickel, palladium, Lindlar's catalyst, cobalt, copper chromite, platinium, platinum oxide, rhenium, tin(II) chloride, titanium(III) chloride, zinc, samarium, iron and mixtures thereof.
  • the hydrogen pressure may be in a range from about atmospheric pressure to about 2,000 psig, alternatively from about 50 psig to about 60 psig.
  • the solvent may be selected from the group consisting of water, petroleum ether, pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1,4-dioxane, chloroform, diethyl ether, dichloromethane, tetrahydrofuran, methyl-tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, n-butanol, isopropanol, n-propanol, ethanol, methanol, and mixtures thereof.
  • the solvent may be ethyl acetate.
  • the compound of formula (IV) may be transformed into the salt of formula (V) in the presence of mHZ and a solvent.
  • R 1 , R 2 , R 3 , R 5 , R 6 , and R 7 are as defined previously, may be independently selected, and may be identical or different.
  • the symbol "m” is the number of moles of the acid. HZ may be selected from the group consisting of D,L-malic acid, L-malic acid, D-malic acid, hydrochloric acid, hydrobromic acid, citric acid, acetic acid, lactic acid, succinic acid, tartaric acid, sulfuric acid, and mixtures thereof; and m may be 1 ⁇ 2, 1, 3/2, or 2.
  • a protecting group may be used when performing the above process.
  • Protecting groups are widely used in chemistry and one skilled in the art would determine the appropriate step during the process to remove the protecting group in order to reach compounds of formula (IV).
  • General explanations and uses of protecting groups are described in "Greene's Protective Groups in Organic Synthesis” by Peter G. M. Wuts, Theodora W. Greene, Wiley- Interscience; 4th edition (October 30, 2006) and in “Protecting Groups” by Philip J. Kocienski, Thieme, Stuttgart; Auflage: 3rd Revised edition (February 14, 2005).
  • Compounds of formula (IV) include 2-methoxymethyl- 1 ,4-benzenediamine (IV-a).
  • the process described above can be utilized to synthesize 2-methoxymethyl- 1 ,4-benzenediamine (IV-a).
  • the process may comprise:
  • Example 1 illustrates the present invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

A process has been developed for preparing 2-methoxymethyl-1,4-benzenediamine (IV-a), other compounds of formula (IV), and the salts thereof, all of which may be used as primary intermediates in compositions for dyeing keratin fibers.

Description

PROCESS FOR PREPARING 2-METHOXYMETHYL-1 ,4-BENZENEDIAMINE
AND SALTS THEREOF
FIELD OF THE INVENTION
The present invention relates to a process for preparing primary intermediates for dyeing keratin fibers. More particularly, the invention relates to a process for preparing 2- methoxymethyl-l,4-benzenediamine (IV-a), other compounds of formula (IV), and the salts thereof.
BACKGROUND OF THE INVENTION
Primary intermediates are used in compositions for dyeing keratin fibers. Known primary intermediates include 2-methoxymethyl-l,4-benzenediamine (IV-a), other compounds of formula (IV), and the salts thereof.
Known processes of preparing 2-methoxymethyl-l,4-benzenediamine (IV-a), other compounds of formula (IV), and the salts thereof have yield and cost deficiencies. Therefore, there is a need for an industrially applicable, less expensive, and higher yielding process to synthesize 2-methoxymethyl-l,4-benzenediamine (IV-a), other compounds of formula (IV), and the salts thereof.
SUMMARY OF THE INVENTION
According to one embodiment of the invention, there is provided a process for the preparation of 2-methoxymethyl-l,4-benzenediamine (IV-a), other compounds of formula (IV), and the salts thereof comprising (a) performing a carbonyl reduction of a compound of formula (I) to prepare a compound of formula (II); (b) performing an etherification of the compound of formula (II) to prepare a compound of formula (III); and (c) performing a hydrogenation of the compound of formula (III) to prepare a compound of formula (IV):
wherein R1, R2, and R3 are substituents selected from the group consisting of:
a) C-linked substituents selected from the group consisting of:
i. alkyl groups;
ii. aryl groups; and
iii. substituents selected from the group consisting of COOA1, CONA1, CONA^OA2, C(=NA1)NA1A2, and CN;
wherein the C-linked substituents comprise from 1 to about 10 carbon atoms and from 0 to about 5 heteroatoms selected from the group consisting of O, F, CI, N, P, Si, and mixtures thereof;
b) S-linked substituents selected from the group consisting of SA1, SO2A1, SO3A1, SSA1, SOA1, SOzNA , SNA1 A2, and SONA ;
c) O-linked substituents selected from the group consisting of OA1, ONA]A2;
d) N-linked substituents selected from the group consisting of NA]A2; (NA1A2A3)+, NA]SA2, N02;
e) halogens selected from the group consisting of F, CI, Br, and I;
f) hydrogen; and
g) mixtures thereof;
wherein A1, A2, and A3 are alkyl groups comprising from 1 to about 10 carbon atoms and from 0 to about 5 heteroatoms selected from the group consisting of O, F, CI, N, P, Si, and mixtures thereof;
wherein R5 is an alkyl group; and
wherein R6 and R7 are selected from the group consisting of hydrogen, alkyl groups, aminoalkyl groups, hydroxyalkyl groups, and mixtures thereof.
This and other features, aspects, and advantages of the present invention will become evident to those skilled in the art from a reading of the present disclosure.
DETAILED DESCRIPTION OF THE INVENTION
In all embodiments of the present invention, all percentages are by weight of the total composition, unless specifically stated otherwise. All ratios are weight ratios, unless specifically stated otherwise. All ranges are inclusive and combinable. The number of significant digits conveys neither a limitation on the indicated amounts nor on the accuracy of the measurements. All numerical amounts are understood to be modified by the word "about" unless otherwise specifically indicated. Unless otherwise indicated, all measurements are understood to be made at 25 °C and at ambient conditions, where "ambient conditions" means conditions under about one atmosphere of pressure and at about 50 % relative humidity. All such weights as they pertain to listed ingredients are based on the active level and do not include carriers or byproducts that may be included in commercially available materials, unless otherwise specified.
The term "comprising," as used herein, means that other steps and other ingredients which do not affect the end result can be added. This term encompasses the terms "consisting of and "consisting essentially of." Compositions and methods/processes of the present invention can comprise, consist of, and consist essentially of the elements and limitations of the invention described herein, as well as any of the additional or optional ingredients, components, steps, or limitations described herein.
The terms "include," "includes," and "including," as used herein, are meant to be non- limiting and are understood to mean "comprise," "comprises," and "comprising," respectively. It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.
The process for the preparation of 2-methoxymethyl- 1 ,4-benzenediamine (IV-a), other compounds of formula (IV), and the salts thereof comprises (a) performing a carbonyl reduction of a compound of formula (I) to prepare a compound of formula (II); (b) performing an etherification of the compound of formula (II) to prepare a compound of formula (III); and (c) performing a hydrogenation of the compound of formula (III) to prepare a compound of formula (IV).
In an embodiment, the carbonyl reduction, then etherification, and then hydrogenation may be performed successively. In another embodiment, the carbonyl reduction, then hydrogenation, and then etherification may be performed successively. I. Carbonyl Reduction
Carbonyl reduction may be performed on a compound of formula (I) to prepare a compound of formula (II). R1, R2, R3, R6, and R7 are as defined previously, may be independently selected, and may be identical or different. Carbonyl reduction may be performed in the presence of a carbonyl reducing agent, a carbonyl reduction catalyst, and/or a solvent.
The carbonyl reducing agent may be selected from the group consisting of hydrazine, hydrazine hydrate, H2, LiAlH4, LiBH4, DIBAL-H, NaBH4, NaCNBH3, B2H6, BH3/THF, sodium hydrosulfite, sodium sulfide, and mixtures thereof.
The carbonyl reduction catalyst may be selected from the group consisting of Raney nickel, nickel, palladium, Lindlar's catalyst, cobalt, copper chromite, platinum, platinum oxide, rhenium, tin(II) chloride, titanium(III) chloride, zinc, samarium, iron, ruthenium, iridium, rhodium, and mixtures thereof.
The solvent may be selected from the group consisting of water, petroleum ether, pentane, acetic acid, cyclopentane, hexane, cyclohexane, benzene, toluene, 1,4-dioxane, chloroform, diethyl ether, dichloromethane, tetrahydrofuran, methyl-tetrahydrofuran, dimethylformamide, acetonitrile, dimethyl sulfoxide, n-butanol, isopropanol, n-propanol, ethanol, methanol, and mixtures thereof.
Carbonyl reduction may be carried out at a temperature of from about 0°C to about
100°C, alternatively from about 50 °C to about 80 °C, alternatively at about 70°C.
In an embodiment, the formula indicated by formula (I) may be prepared by inserting a nitro function into anthranilic acid or compounds thereof in the presence of a nitrating agent and/or a solvent. The nitrating agent may be selected from the group consisting of nitric acid, fuming nitric acid, red fuming nitric acid, salts of nitric acid (i.e. potassium nitrate), and mixtures thereof.
(I)
II. Etherification
Etherification may be performed on the compound of formula (II) to prepare a compound of formula (III). R1, R2, R3, R5, R6, and R7 are as defined previously, may be independently selected, and may be identical or different. Alkylation Reaction
Etherification may be performed by an alkylation reaction in the presence of an alkylating agent, a phase transfer catalyst, a solvent, and/or a base. The reaction mixture may be homogeneous or heterogeneous, may have two or more liquid phases, and/or may have any combination of liquid and solid phases.
The alkylating agent may be selected from the group consisting of alcohols, derivatives of alcohols (i.e. methyl methanesulfonate), (Ci-C4)-I, (Ci-C4)-Br, (Ci-C4)-Cl, Me2S04, and mixtures thereof. In one embodiment, the alkylating agent may be dimethyl sulfate.
The phase transfer catalyst may be selected from the group consisting of ammonium salts that include tetrapentylammonium bromide, tetraoctylammonium chloride, tetraoctylammonium bromide, tetrahexylammonium iodide, tetrahexylammonium chloride, tetrahexylammonium bromide, tetraheptylammonium bromide, tetraethylammonium tetrafluoroborate, tetraethylammonium chloride, tetraethylammonium bromide, tetradodecylammonium tetrafluoroborate, tetradodecylammonium chloride, tetradodecylammonium bromide, tetradecyl- trimethylammonium chloride, benzyltriethyl ammonium chloride, phenyl-trimethylammonium bromide, octyl-trimethylammonium bromide, octadecyl-trimethylammonium chloride, octadecyl-trimethylammonium bromide, methyl-trioctylammonium iodide, and mixtures thereof. In one embodiment, the phase transfer catalyst may be benzyltriethyl ammonium chloride.
The solvent may be selected from the group consisting of water, petroleum ether, pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1,4-dioxane, chloroform, diethyl ether, dichloromethane, tetrahydrofuran, methyl-tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, n-butanol, isopropanol, n-propanol, ethanol, methanol, and mixtures thereof.
The base may be selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, aluminum hydroxide, ferrous hydroxide, ferric hydroxide, zinc hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, and mixtures thereof. In one embodiment, the base may be sodium hydroxide. Condensation Reaction
Etherification may also be performed by a condensation reaction in the presence of a condensation catalyst and/or a solvent. The condensation catalyst may be selected from the group consisting of mineral acids, Lewis Acids, aluminum chloride, titanium tetra-isopropoxide, and mixtures thereof.
The solvent may be selected from the group consisting of petroleum ether, pentane, cyclopentane, hexane, acetic acid, cyclohexane, benzene, toluene, 1,4-dioxane, chloroform, diethyl ether, dichloromethane, tetrahydrofuran, methyl-tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, n-butanol, isopropanol, n-propanol, ethanol, methanol, and mixtures thereof. In one embodiment, the solvent may be methanol.
The condensation reaction may be carried out with an inert solvent diluent and/or with heating. The inert solvent diluent may be chosen to aid in the removal of water if it is capable of forming a low boiling azeotrope. In this case, the condensation reaction may be carried out at reflux using a Dean Stark trap to drain off the water as it is formed and distilled off with the azeotrope. The condensation reaction may also be carried out in the presence of one or more dehydrating agents which may either react with or physically bind with the water, thereby removing the water from equilibria. The dehydrating agent may be selected from the group consisting of dicyclohexylcarbodiimide, molecular sieves, magnesium sulphate, and mixtures thereof.
III. Hydro2enation
Hydrogenation may be performed on the compound of formula (III) to prepare a compound of formula (IV). R1, R2, R3, R5, R6, and R7 are as defined previously, may be independently selected, and may be identical or different.
Hydrogenation may be performed in the presence of hydrogen, a hydrogenation catalyst, and/or a solvent. The hydrogenation catalyst may be selected from the group consisting of Raney nickel, nickel, palladium, Lindlar's catalyst, cobalt, copper chromite, platinium, platinum oxide, rhenium, tin(II) chloride, titanium(III) chloride, zinc, samarium, iron and mixtures thereof. The hydrogen pressure may be in a range from about atmospheric pressure to about 2,000 psig, alternatively from about 50 psig to about 60 psig.
The solvent may be selected from the group consisting of water, petroleum ether, pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1,4-dioxane, chloroform, diethyl ether, dichloromethane, tetrahydrofuran, methyl-tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, n-butanol, isopropanol, n-propanol, ethanol, methanol, and mixtures thereof. In an embodiment, the solvent may be ethyl acetate. In an embodiment, the compound of formula (IV) may be transformed into the salt of formula (V) in the presence of mHZ and a solvent. R1, R2, R3, R5, R6, and R7 are as defined previously, may be independently selected, and may be identical or different.
HZ is an acid having an acid proton "H." "Z" represents the rest of the molecule. For example if HZ = HC1, then Z = CI. The symbol "m" is the number of moles of the acid. HZ may be selected from the group consisting of D,L-malic acid, L-malic acid, D-malic acid, hydrochloric acid, hydrobromic acid, citric acid, acetic acid, lactic acid, succinic acid, tartaric acid, sulfuric acid, and mixtures thereof; and m may be ½, 1, 3/2, or 2.
Protecting Groups
In an embodiment, a protecting group may be used when performing the above process. Protecting groups are widely used in chemistry and one skilled in the art would determine the appropriate step during the process to remove the protecting group in order to reach compounds of formula (IV). General explanations and uses of protecting groups are described in "Greene's Protective Groups in Organic Synthesis" by Peter G. M. Wuts, Theodora W. Greene, Wiley- Interscience; 4th edition (October 30, 2006) and in "Protecting Groups" by Philip J. Kocienski, Thieme, Stuttgart; Auflage: 3rd Revised edition (February 14, 2005). IV. Synthesis of 2-Methoxymethyl-l,4-Benzenediamine
Compounds of formula (IV) include 2-methoxymethyl- 1 ,4-benzenediamine (IV-a). The process described above can be utilized to synthesize 2-methoxymethyl- 1 ,4-benzenediamine (IV-a). The process may comprise:
a) reducing the carbonyl group of 5-nitroanthranilic acid (I-a) to prepare 2-amino-5- nitrobenzyl alcohol (Il-a);
b) performing the etherification of 2-amino-5-nitrobenzyl alcohol (Il-a) to prepare 2- methoxymethyl-4-nitroaniline (Ill-a); and c) hydrogenating 2-methoxymethyl-4-nitroaniline (Ill-a) to prepare 2-methoxymethyl- 1,4-benzenediamine (IV-a).
(1-a) (Il-a) (Ill-a) (IV-a)
EXAMPLES
The following examples illustrate the present invention: Example 1
1. Synthesis of 2-Hvdroxymethyl-4-Nitroaniline (Il-a)
5-Nitroanthranilic acid (5.0 g, 27.45 mmol) is dissolved in THF (100 mL) and 1 M borane/THF complex (55 mL, 54.9 mmol) is added. The mixture is heated to reflux for 1 h. Analysis by TLC indicates complete consumption of starting material. The volatiles are removed in vacuo and the residue is dissolved in ethyl acetate (150 mL). The organic phase is washed with 1 N HC1, saturated NaHCC>3, and saturated NaCl. Evaporation provides 10.8 g (98%) of a dark brown oil product which is used directly in the next reaction; ^-NMR (500 MHz, CDC13); δ 4.61 (s, 2 H), 6.62 (s, 1 H), 8.01 (m, 2 H).
2. Synthesis of 2-Methoxymethyl-4-Nitroaniline (Ill-a)
2-Hydroxymethyl-4-nitroanilne (1.0 g, 5.75 mmol) is suspended in petroleum ether (10 mL). Sodium hydroxide solution (50%, 618 mg, 15.46 mmol) and benzyltriethylammonium chloride (20 mg) are added with stirring. Dimethyl sulfate (728 uL, 7.7 mmol) is added and the reaction mixture is stirred at room temperature for 16 hours. Dichloromethane (50 mL) and water (25 mL) are added, and the layers are separated. The organic layer is washed with saturated NaHCC>3 and evaporated affording 440 mg of 2-methoxymethyl-4-nitroaniline (Ill-a) in 82% purity. 3. Synthesis of 2-Methoxymethyl-l,4-Benzenediamine (IV-a)
Into a Parr hydrogenation bottle previously purged with argon, are placed a solution of 2- methoxymethyl-4-nitroaniline (5.0 g, 27.5 mmol) in ethyl acetate (50 mL) and 0.25 g of 10% palladium on carbon. The bottle is mounted on a Parr shaker and hydrogenation is carried out under 50 - 60 psig (64.7 - 74.7 psi or 446 - 515 kPa) of hydrogen pressure. The pressure is carefully monitored for hydrogen uptake and additional hydrogen is introduced to keep the pressure above 50 psig. The hydrogenation is carried out for 3.5 hours after which the catalyst is removed by vacuum filtration. The filtrate is concentrated to about 25 mL and toluene (25 mL) is added to precipitate the product, which is collected by vacuum filtration and dried at 60° C under vacuum. The product yield is 4.5 g; ^-NMR (500 MHz, DMSO- ) δ 3.23 (s, 3 H), 4.11 (s, 2 H), 4.21 (s, 2 H), 4.24 (s, 2 H), 6.33 (dd, 1 H), 6.37 (d, 1 H), 6.41 (d, 1 H).
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."
Every document cited herein, including any cross referenced or related patent or application, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests, or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.
While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover all such changes and modifications that are within the scope of this invention.

Claims

CLAIMS What is claimed is:
1. A process for the preparation of 2-methoxymethyl-l,4-benzenediamine (IV-a), other compounds of formula (IV), and the salts thereof comprising:
a. performing a carbonyl reduction of a compound of formula (I) to prepare a compound of formula (II);
b. performing an etherification of the compound of formula (II) to prepare a compound of formula (III); and
c. performing a hydrogenation of the compound of formula (III) to prepare a compound of formula (IV);
wherein R1, R2, and R3 are substituents selected from the group consisting of:
i. C-linked substituents selected from the group consisting of:
a) alkyl groups;
b) aryl groups; and
c) substituents selected from the group consisting of COOA1, CONA1,
CONA^OA2, C(=NA1)NA1A2, and CN;
wherein the C-linked substituents comprise from 1 to 10 carbon atoms and from 0 to 5 heteroatoms selected from the group consisting of O, F, CI, N, P, Si, and mixtures thereof;
ii. S-linked substituents selected from the group consisting of SA1, SO2A1, SO3A1, SSA1, SOA1, SOzNA^2, SNA1 A2, and SONA^2;
iii. O-linked substituents selected from the group consisting of OA1, ONA]A2; iv. N-linked substituents selected from the group consisting of NA]A2; (NA1A2A3)+, NA]SA2, N02;
v. halogens selected from the group consisting of F, CI, Br, and I;
vi. hydrogen; and
vii. mixtures thereof;
wherein A1, A2, and A3 are alkyl groups comprising from 1 to 10 carbon atoms and from 0 to 5 heteroatoms selected from the group consisting of O, F, CI, N, P, Si, and mixtures thereof;
wherein R5 is an alkyl group; and
wherein R6 and R7 are selected from the group consisting of hydrogen, alkyl groups, aminoalkyl groups, hydroxyalkyl groups, and mixtures thereof.
2. The process according to claim 1 further comprising inserting a nitro function into anthranilic acid or compounds thereof in the presence of a nitrating agent and a solvent to prepare the compound of formula (I):
3. The process according to claim 1 or 2, wherein the carbonyl reduction of the compound of formula (I) into the compound of formula (II) is performed in the presence of a carbonyl reducing agent, a carbonyl reduction catalyst, and a solvent.
4. The process according to claim 3, wherein the carbonyl reducing agent is selected from the group consisting of hydrazine, hydrazine hydrate, H2, LiAlH4, L1BH4, DIBAL-H, NaBH4, NaCNB]¾, B2H6, BH3/THF, sodium hydrosulfite, sodium sulfide, and mixtures of thereof.
5. The process according to claim 3 or 4, wherein the carbonyl reduction catalyst is selected from the group consisting of Raney nickel, nickel, palladium, Lindlar' s catalyst, cobalt, copper chromite, platinium, platinum oxide, rhenium, tin(II) chloride, titanium(III) chloride, zinc, samarium, iron and mixtures thereof.
6. The process according to any preceding claim, wherein the etherification of the compound of formula (II) into the compound of formula (III) is performed by alkylation in the presence of an alkylating agent, a phase transfer catalyst, a solvent, and a base.
7. The process according to claim 6, wherein the alkylating agent is selected from the group consisting of methanol, (CrC4)-I, (CrC4)-Br, (Ci-C4)-Cl, Me2S04, and mixtures thereof.
8. The process according to claim 6 or 7, wherein the phase transfer catalyst is selected from the group consisting of ammonium salts that include tetrapentylammonium bromide, tetraoctylammonium chloride, tetraoctylammonium bromide, tetrahexylammonium iodide, tetrahexylammonium chloride, tetrahexylammonium bromide, tetraheptylammonium bromide, tetraethylammonium tetrafluoroborate, tetraethylammonium chloride, tetraethylammonium bromide, tetradodecylammonium tetrafluoroborate, tetradodecylammonium chloride, tetradodecylammonium bromide, tetradecyl-trimethylammonium chloride, benzyltriethyl ammonium chloride, phenyl-trimethylammonium bromide, octyl-trimethylammonium bromide, octadecyl-trimethylammonium chloride, octadecyl-trimethylammonium bromide, methyl- trioctylammonium iodide, and mixtures thereof.
9. The process according to claim 6, 7, or 8, wherein the base is selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, aluminum hydroxide, ferrous hydroxide, ferric hydroxide, zinc hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, and mixtures thereof.
10. The process according to any preceding claim, wherein the etherification of the compound of formula (II) into the compound of formula (III) is performed by a condensation reaction in the presence of a condensation catalyst and a solvent.
11. The process according to claim 10, wherein the condensation catalyst is selected from the group consisting of mineral acids, Lewis Acids, aluminum chloride, titanium tetra-isopropoxide, and mixtures thereof.
12. The process according to any preceding claim, wherein the hydrogenation of the compound of formula (III) into the compound of formula (IV) is performed in the presence of hydrogen, a hydrogenation catalyst, and a solvent.
13. The process according to claim 12, wherein the hydrogenation catalyst is selected from the group consisting of Raney nickel, nickel, palladium, Lindlar' s catalyst, cobalt, copper chromite, platinium, platinum oxide, rhenium, tin(II) chloride, titanium(III) chloride, zinc, samarium, iron and mixtures thereof.
14. The process according to any preceding claim, further comprising transforming the compound of formula (IV), including 2-methoxymethyl-l,4-benzenediamine (IV-a), into the salt of formula (V) in the presence of mHZ and a solvent:
15. The process according to claim 14, wherein HZ is selected from the group consisting of D,L-malic acid, L-malic acid, D-malic acid, hydrochloric acid, hydrobromic acid, citric acid, acetic acid, lactic acid, succinic acid, tartaric acid, sulfuric acid, and mixtures thereof; and wherein m = 1.
EP13786397.3A 2012-10-26 2013-10-25 Process for preparing 2-methoxymethyl-1,4-benzenediamine and salts thereof Withdrawn EP2912009A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201261718961P 2012-10-26 2012-10-26
PCT/US2013/066729 WO2014066713A1 (en) 2012-10-26 2013-10-25 Process for preparing 2-methoxymethyl-1,4-benzenediamine and salts thereof

Publications (1)

Publication Number Publication Date
EP2912009A1 true EP2912009A1 (en) 2015-09-02

Family

ID=49519147

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13786397.3A Withdrawn EP2912009A1 (en) 2012-10-26 2013-10-25 Process for preparing 2-methoxymethyl-1,4-benzenediamine and salts thereof

Country Status (5)

Country Link
US (1) US9309185B2 (en)
EP (1) EP2912009A1 (en)
CN (1) CN104768917A (en)
MX (1) MX2015004989A (en)
WO (1) WO2014066713A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9210521B2 (en) 2012-07-16 2015-12-08 Sophono, Inc. Abutment attachment systems, mechanisms, devices, components and methods for bone conduction hearing aids
CN104478833A (en) * 2014-11-24 2015-04-01 苏州乔纳森新材料科技有限公司 Synthetic method of (S)-(+)-3-hydroxytetrahydrofuran
US20170158608A1 (en) * 2015-12-03 2017-06-08 The Procter & Gamble Company Process for the Preparation of 2-Alkoxymethyl-1,4-Benzenediamines
WO2018064245A1 (en) * 2016-09-29 2018-04-05 Shell Oil Company Method for acid treatment conditioning of a catalyst in the production of glycols

Family Cites Families (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2273564A (en) 1939-04-21 1942-02-17 Eastman Kodak Co Diamino benzyl alcohols and process for making same
US2528378A (en) 1947-09-20 1950-10-31 John J Mccabe Jr Metal salts of substituted quaternary hydroxy cycloimidinic acid metal alcoholates and process for preparation of same
US2781354A (en) 1956-03-26 1957-02-12 John J Mccabe Jr Imidazoline derivatives and process
DE3524329A1 (en) 1985-07-08 1987-01-08 Henkel Kgaa NEW AMINOPHENOLS AND THEIR USE IN OXIDATION HAIR COLORING AGENTS
DE3914253A1 (en) 1989-04-29 1990-10-31 Wella Ag OXIDATING HAIR AGENTS BASED ON 4-AMINOPHENOL DERIVATIVES AND NEW 4-AMINOPHENOL DERIVATIVES
DE19957282C1 (en) * 1999-11-29 2001-05-17 Wella Ag Process for the preparation of 1,4-diamino-2-methoxymethyl-benzene and its salts
DE10000460B4 (en) 2000-01-07 2004-05-06 Wella Aktiengesellschaft Means and processes for coloring hair
DE10032135B4 (en) 2000-07-01 2004-06-03 Wella Ag Agent containing 2,4-diamino-1- (2-methoxyethoxy) benzene and process for coloring human hair
DE20107481U1 (en) 2001-05-02 2001-07-12 Wella Ag Means for coloring keratin fibers
US7591860B2 (en) 2004-02-27 2009-09-22 L'oreal, S.A. N-alkylpolyhydroxylated secondary para-phenylenediamines, dye compositions comprising them, processes, and uses thereof
DE102004031590A1 (en) 2004-06-30 2006-02-16 Henkel Kgaa Phenylpropandiol dye products
CA2576189A1 (en) 2007-01-29 2007-06-11 The Procter & Gamble Company Hair dyes comprising 1,4-diamino-2-methoxymethylbenzene
CN102149697A (en) * 2008-09-08 2011-08-10 弗·哈夫曼-拉罗切有限公司 6-substituted benzoxazines as 5-HT-5A receptor antagonists
DE102008061864A1 (en) 2008-12-15 2010-10-21 Henkel Ag & Co. Kgaa Agent, useful for oxidative coloring of keratin fibers e.g. human hair, comprises p-phenylene diamine derivatives, as developer component, in a carrier
CA2759451C (en) 2009-04-20 2014-10-07 The Procter & Gamble Company Keratin dyeing compositions comprising a radical scavenger and use thereof
EP2421613A2 (en) 2009-04-20 2012-02-29 The Procter & Gamble Company Keratin dyeing compositions comprising a radical scavenger and a chelant and use thereof
FR2945742B1 (en) 2009-05-19 2012-08-17 Oreal TINCTORIAL COMPOSITION COMPRISING A PARA-PHENYLENE DIAMINE SECONDARY OXIDATION BASE AND A SELECTED BENZENIC COUPLER
WO2010133640A2 (en) 2009-05-19 2010-11-25 L'oreal Dyeing composition comprising a secondary para-phenylenediamine oxidation base and a heterocyclic oxidation base
WO2010139878A2 (en) 2009-05-19 2010-12-09 L'oreal Dyeing composition including a secondary paraphenylenediamine oxidation base and a selected coupler
FR2945737B1 (en) 2009-05-19 2011-06-10 Oreal TINCTORIAL COMPOSITION COMPRISING A SECONDARY PARA-PHENYLENE DIAMINE OXIDATION BASE AND A PARTICULAR PARA-AMINO PHENOL OXIDATION BASE
WO2010133639A1 (en) 2009-05-19 2010-11-25 L'oreal Dyeing composition comprising a secondary para-phenylenediamine oxidation base and a selected para-phenylenediamine or para-aminophenol oxidation base
WO2010133575A2 (en) 2009-05-19 2010-11-25 L'oreal Dyeing composition comprising a secondary para-phenylenediamine oxidation base and a silicone fatty substance or a non-silicone liquid fatty substance
FR2945734B1 (en) 2009-05-19 2011-06-17 Oreal TINCTORIAL COMPOSITON COMPRISING THE PARA-PHENYLENE DIAMINE SECONDARY OXIDATION BASE AND A NACRANT AGENT.
FR2945728B1 (en) 2009-05-19 2012-10-19 Oreal TINCTORIAL COMPOSITION COMPRISING A SECONDARY PARA-PHENYLENE DIAMINE OXIDATION BASE AND A NON-ASSOCIATIVE ACRYLIC THERAPY ANIONIC POLYMER.
FR2945739B1 (en) 2009-05-19 2011-07-29 Oreal TINCTORIAL COMPOSITION COMPRISING A PARA-PHENYLENE DIAMINE SECONDARY OXIDATION BASE AND AN AMINOPYRAZOLOPYRIDINE OXIDATION BASE
FR2945727B1 (en) 2009-05-19 2012-08-24 Oreal TINCTORIAL COMPOSITION COMPRISING A PARA-PHENYLENE DIAMINE SECONDARY OXIDATION BASE AND A CATIONIC POLYMER
FR2945732B1 (en) 2009-05-19 2011-06-17 Oreal TINCTORIAL COMPOSITION COMPRISING A PARA-PHENYLENE DIAMINE SECONDARY OXIDATION BASE AND CATIONIC CHARGE SURFACTANT.
FR2945743B1 (en) 2009-05-19 2012-09-07 Oreal TINCTORIAL COMPOSITION COMPRISING A PARA-PHENYLENE DIAMINE SECONDARY OXIDATION BASE AND SELECTED COUPLER
FR2945731B1 (en) 2009-05-19 2011-06-10 Oreal TINCTORIAL COMPOSITION COMPRISING A PARA-PHENYLENE DIAMINE SECONDARY OXIDATION BASE AND SILICONE
FR2945729B1 (en) 2009-05-19 2012-10-19 Oreal TINCTORIAL COMPOSITION COMPRISING A SECONDARY PARA-PHENYLENE DIAMINE OXIDATION BASE AND A NON-CATIONIC NON-ASSOCIATIVE POLYMER WITH SUGAR MOTIFS.
WO2010133573A2 (en) 2009-05-19 2010-11-25 L'oreal Dyeing composition comprising a secondary para-phenylenediamine oxidation base and a thickening polymer
FR2945735B1 (en) 2009-05-19 2011-06-17 Oreal TINCTORIAL COMPOSITION COMPRISING A PARA-PHENYLENE DIAMINE SECONDARY OXIDATION BASE AND A PARTICULAR NON-IONIC SURFACTANT
FR2945738B1 (en) 2009-05-19 2011-07-22 Oreal TINCTORIAL COMPOSITION COMPRISING A PARA-PHENYLENE DIAMINE SECONDARY OXIDATION BASE AND AN AMINO ACID
FR2945726B1 (en) 2009-05-19 2011-06-10 Oreal TINCTORIAL COMPOSITION COMPRISING A SECONDARY PARA-PHENYLENE DIAMINE OXIDATION BASE AND A NONIONIC, ANIONIC OR CATIONIC ASSOCIATIVE POLYMER
WO2010133803A1 (en) 2009-05-19 2010-11-25 L'oreal Dyeing composition comprising a secondary para-phenylenediamine oxidation base and a specific surfactant
FR2945736B1 (en) 2009-05-19 2011-06-10 Oreal TINCTORIAL COMPOSITION COMPRISING A SECONDARY PARA-PHENYLENE DIAMINE OXIDATION BASE AND A SELECTED PARA-PHENYLENE DIAMINE OXIDATION BASE
FR2945740B1 (en) 2009-05-19 2011-06-10 Oreal TINCTORIAL COMPOSITION COMPRISING A PARA-PHENYLENE DIAMINE SECONDARY OXIDATION BASE AND DIAMINOPYRAZOLE OXIDATION BASE
FR2945741B1 (en) 2009-05-19 2011-06-10 Oreal TINCTORIAL COMPOSITION COMPRISING A PARA-PHENYLENE DIAMINE SECONDARY OXIDATION BASE AND A DIAMINOPYRAZOLINONE BASE
FR2945744B1 (en) 2009-05-19 2011-06-10 Oreal TINCTORIAL COMPOSITION COMPRISING A SECONDARY PARA-PHENYLENE DIAMINE OXIDATION BASE AND A 4-FORMYL-1-METHYLQUINOLINIUM SALT
FR2945733B1 (en) 2009-05-19 2012-08-10 Oreal TINCTORIAL COMPOSITION COMPRISING A PARA-PHENYLENE DIAMINE SECONDARY OXIDATION BASE AND A CARBOXYLIC ETHER ACID
FR2945730B1 (en) 2009-05-19 2012-10-19 Oreal TINCTORIAL COMPOSITION COMPRISING A PARA-PHENYLENE DIAMINE SECONDARY OXIDATION BASE AND A NON-SILICONE LIQUID FATTY BODY
FR2945756B1 (en) 2009-05-20 2011-08-05 Commissariat Energie Atomique NANOCOMPOSITE SOLID MATERIAL BASED ON HEXA AND OCTACYANOMETALLATES, PROCESS FOR PREPARING THE SAME, AND METHOD FOR FIXING MINERAL POLLUTANTS USING THE SAME
FR2946647B1 (en) 2009-06-11 2011-06-24 Oreal AZOMETHINIC DIRECT COLORANTS OR REDUCED PRECURSORS OF THESE COLORANTS OBTAINED FROM N-ALKYLAMINE SECONDARY PARA-PHENYLENEDIAMINES, CAPILAR COLORING PROCESS FROM THESE COLORANTS.
FR2946648A1 (en) 2009-06-11 2010-12-17 Oreal AZOMETHINIC DIRECT DYES N-OXIDES OR REDUCED PRECURSORS OF THESE COLORANTS OBTAINED FROM N-ALKYLAMINE SECONDARY PARA-PHENYLENEDIAMINES, CAPILAR COLORING PROCESS FROM THESE DYES.
CN103140465B (en) 2010-09-29 2015-09-02 宝洁公司 The method of synthesis 2-methoxymethyl-Isosorbide-5-Nitrae-phenylenediamine
MX2013003692A (en) * 2010-09-29 2013-05-09 Procter & Gamble Methods of synthesizing 2- substituted-1,4-benzenediamine.
WO2012074536A1 (en) 2010-12-03 2012-06-07 The Procter & Gamble Company Process for the preparation of 2-methoxymethyl-1,4-benzenediamine, its derivatives thereof and the salts thereof
MX2013009690A (en) 2011-02-22 2013-12-06 Procter & Gamble Oxidative dyeing compositions comprising an 1-hexyl/heptyl-4,5-di aminopyrazole and a benzene-1,3-diamine and derivatives thereof.
EP2677989A1 (en) 2011-02-22 2014-01-01 The Procter and Gamble Company Oxidative dyeing compositions comprising an 1-hexyl/heptyl-4,5-diaminopyrazole and a benzene-1,3-diol and derivatives thereof
WO2013085554A2 (en) 2011-02-22 2013-06-13 The Procter & Gamble Company Oxidative dyeing compositions comprising an 1-hexyl/heptyl-4,5-diaminopyrazole and a naphthalen-1-ol and derivatives thereof
EP2677993B1 (en) 2011-02-22 2018-08-22 Noxell Corporation Oxidative dyeing compositions comprising an 1-hexyl/heptyl-4,5-diaminopyrazole and a m-aminophenol and derivatives thereof
CN103379939B (en) 2011-02-22 2016-12-07 宝洁公司 Comprise the oxidative dye compositions of 1 hexyl/heptyl 4,5 diamino-pyrazole and pyridine and its derivatives
MX336132B (en) 2011-02-22 2016-01-07 Procter & Gamble Oxidative dyeing compositions comprising an 1-hexyl/heptyl-4,5-di aminopyrazole and a benzo[1,3]dioxol-5-ylamine and derivatives thereof.
WO2013058816A1 (en) 2011-02-22 2013-04-25 The Procter & Gamble Company Oxidative dyeing compositions comprising an 1-hexyl/heptyl-4,5-diaminopyrazole and a 2-aminophenol and derivatives thereof
US8529637B2 (en) 2011-09-30 2013-09-10 The Procter & Gamble Company Foam oxidative hair colorant composition with the free-base of 1,4-diamino-2-methoxymethyl benzene
EP2912008B1 (en) * 2012-10-26 2020-08-05 Noxell Corporation Process for preparing 2-methoxymethyl-1,4-benzenediamine and salts thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2014066713A1 *

Also Published As

Publication number Publication date
US20140121415A1 (en) 2014-05-01
MX2015004989A (en) 2015-07-17
CN104768917A (en) 2015-07-08
US9309185B2 (en) 2016-04-12
WO2014066713A1 (en) 2014-05-01

Similar Documents

Publication Publication Date Title
US9012691B2 (en) Process for preparing primary intermediates for dyeing keratin fibers
US8592631B2 (en) Process for the preparation of 2-methoxymethy1-1,4-benzenediamine, its derivatives thereof and the salts thereof
JP6441478B2 (en) Process for preparing disubstituted 1,4-benzenediamine and salts thereof
US9309185B2 (en) Process for preparing primary intermediates for dyeing keratin fibers
EP2621888A1 (en) Methods of synthesizing 2- substituted-1,4-benzenediamine
CN102421746B (en) Process for the preparation of ethylene glycol and related compounds
EP3201171B1 (en) Method of preparing intermediate of salmeterol
CN110885292A (en) Synthetic method of β-amino alcohol compounds
CN106748826B (en) N, N, N '-trimethyl-N '-ethoxy-ethylenediamine the preparation method
JP6999112B2 (en) 2,5-Bis (aminomethyl) furan dihalogenated hydrogen salt and its production method, and 2,5-bis (aminomethyl) furan production method.
CA2759341C (en) Low-voc polyamines
JP5645494B2 (en) Method for producing amine body
WO2014008639A1 (en) Method for preparing indacaterol
CN111302962A (en) Rapid method for reducing nitro in aliphatic nitro compound into amino
US9346826B2 (en) Process for producing an intermediate for a cyclic carbodiimide compound
WO2004050604A2 (en) Process for preparing terbinafine by using platinum as catalyst
WO2014083223A1 (en) Method for obtaining secondary amines from nitrobenzene in a single reactor
CN108699009A (en) The method for preparing 3- piperazines -1- bases-propylamine derivatives
WO2009144517A1 (en) Process for the preparation of cyclohexanol derivatives
HK1262579A1 (en) Process for the manufacture of 3-piperazin-1-yl-propylamine derivatives
CA2775388A1 (en) Method for preparing polyamine compounds

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20150325

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

RIN1 Information on inventor provided before grant (corrected)

Inventor name: PATTEN, MONICA, JO

Inventor name: GARRETT, GARRY, STEVEN

Inventor name: GARDLIK, JOHN, MICHAEL

Inventor name: MURPHY, BRYAN, PATRICK

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: NOXELL CORPORATION

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20190501